EP0643103A1 - Curable binders - Google Patents
Curable binders Download PDFInfo
- Publication number
- EP0643103A1 EP0643103A1 EP94112176A EP94112176A EP0643103A1 EP 0643103 A1 EP0643103 A1 EP 0643103A1 EP 94112176 A EP94112176 A EP 94112176A EP 94112176 A EP94112176 A EP 94112176A EP 0643103 A1 EP0643103 A1 EP 0643103A1
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- EP
- European Patent Office
- Prior art keywords
- binders
- epoxy resin
- molecule
- ethylenically unsaturated
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
Definitions
- the present invention relates to curable binders based on epoxy resin mixtures which are particularly suitable as adhesives curing at room temperature with good adhesion under tensile shear stress.
- Such binders are known from DE-A 41 05 481. This document mentions compositions of epoxy resin components and polyfunctional acrylates, such as. B. polyethylene glycol diacrylate, but which have a deteriorated water resistance due to water absorption.
- the improvement by the invention according to DE-A 41 05 481 consists in the mixing of epoxy resins with aromatic, monofunctional (meth) acrylates.
- the strength under tensile shear stress of these mixtures does not meet the demands placed on a high-quality adhesive or a high-quality binder.
- binders according to claims 1 to 4. These binders are used as binders for dowel and anchor compounds, for sealants and adhesives for the production of insulating glass and as injection resins, according to claims 5 to 7.
- the mixtures When applied to a suitable substrate in the processable state, the mixtures form excellent adhesion to a large number of substrates, such as, for. B. to glass, stone, metal, wood and plastics, in particular to those made of polar molecules, such as. B. PVC, polyester, polyamide, phenolic resin, epoxy resin or polyacrylate.
- substrates such as, for. B. to glass, stone, metal, wood and plastics, in particular to those made of polar molecules, such as. B. PVC, polyester, polyamide, phenolic resin, epoxy resin or polyacrylate.
- binders are therefore suitable as binders for bonding substrates of the same type but also substrates of different types to one another. Even when stored in boiling water for several hours, the binders have a low water absorption. This ensures good water resistance.
- All epoxy compounds with at least two epoxy groups in the molecule can be used as the epoxy resin component for the mixture.
- Polyepoxide compounds based on bisphenols or phenol or cresol novolaks are preferred.
- difunctional aromatic or aliphatic epoxy compounds, so-called reactive thinners can be added to these resins.
- Partial esters of a di- or polyepoxide compound with an ethylenically unsaturated acid are reaction products known per se from epoxy compounds with at least two epoxide groups in the molecule with an ethylenically unsaturated acid.
- Examples of such acids are acrylic, methacrylic, cinnamon or furylacrylic acid.
- the quantitative ratio of epoxy groups to ethylenically unsaturated acid is selected so that the partial ester formed contains on average at least one epoxy and one ethylenically unsaturated group in the molecule.
- Epoxy resin and partial esters of a di- or polyepoxide compound with an ethylenically unsaturated acid are mixed with one another in a weight ratio of from 90:10 to 10:90, preferably from 70:30 to 30:70. These mixtures are stable on storage.
- All compounds containing at least one primary amino group such as. B. aliphatic, alicyclic and aromatic mono-, di- or polyamines but also polyaminoamides.
- the primary amines known from epoxy resin curing, as used, for. B. also described in Lee and Neville "Handbook of Epoxy Resins", McGraw-Hill Book Company 1967.
- the amount of amine is chosen so that an amine hydrogen atom is available for each unsaturated bond and for each epoxy group.
- the ethylenically unsaturated double bonds react very quickly with the amine used as curing agent, and in a further step the im react same molecule and the epoxy groups present in the epoxy resin also with the amine.
- the spontaneous reaction between amine and double bond accelerates the system to such an extent that excellent adhesion values are achieved after a relatively short time.
- the low water absorption which is similar to that of the unmodified epoxy resin systems, can also only be achieved by means of the double functionality, since similarly good values are achieved with aliphatic compounds as otherwise only with aromatic hydrophobic compounds.
- the binders according to the invention are suitable as adhesives and binders for coatings and leveling compounds, especially as binders for dowel and anchor compounds, for sealants and adhesives for insulating glass production and as injection resins.
- both the resin and the hardener components can be mixed with fillers, additives, plasticizers or other polymers.
- the proportions of the two components can be adjusted so that there are favorable mixing ratios.
- common fillers are chalks, silicates or oxides, or oxide hydrates of the elements aluminum, magnesium, silicon or titanium.
- Common additives are thickeners, pigments or silanes, in particular epoxysilanes, which bring about a further improvement in adhesion, in particular on silicate substrates.
- the water absorption after 7 days of hardening and the tensile-shear bond strength are determined from test specimens in accordance with DIN 53 281 from 1.6 mm thick plates made of aerospace aluminum (Al Cu Mg 2 pl).
- a bisphenol A diglycidyl ether resin with an epoxy equivalent weight of 185 g / equivalent is used in all cases as the base epoxy resin.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Formation Of Insulating Films (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Glass Compositions (AREA)
- Reinforced Plastic Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft härtbare Bindemittel auf der Basis von Epoxidharz-Mischungen, die sich insbesondere als bei Raumtemperatur härtende Klebstoffe mit guter Haftung bei Zug-Scherbeanspruchung eignen.The present invention relates to curable binders based on epoxy resin mixtures which are particularly suitable as adhesives curing at room temperature with good adhesion under tensile shear stress.
Derartige Bindemittel sind aus DE-A 41 05 481 bekannt. Diese Schrift erwähnt Zusammensetzungen aus Epoxidharz-Komponenten und polyfunktionellen Acrylaten, wie z. B. Polyethylenglykoldiacrylat, die jedoch infolge Wasseraufnahme eine verschlechterte Wasserwiderstandsfähigkeit haben.Such binders are known from DE-A 41 05 481. This document mentions compositions of epoxy resin components and polyfunctional acrylates, such as. B. polyethylene glycol diacrylate, but which have a deteriorated water resistance due to water absorption.
Die Verbesserung durch die Erfindung gemäß DE-A 41 05 481 besteht in der Abmischung von Epoxidharzen mit aromatischen, monofunktionellen (Meth)acrylaten. Die Festigkeit bei Zug-Scherbeanspruchung dieser Mischungen erfüllen aber nicht die Ansprüche, die an einen hochwertigen Klebstoff, bzw. an ein hochwertiges Bindemittel gestellt werden.The improvement by the invention according to DE-A 41 05 481 consists in the mixing of epoxy resins with aromatic, monofunctional (meth) acrylates. The strength under tensile shear stress of these mixtures does not meet the demands placed on a high-quality adhesive or a high-quality binder.
Es ist daher Aufgabe der vorliegenden Erfindung, bei Raumtemperatur härtbare Bindemittel bereitzustellen, die in relativ kurzer Zeit aushärten, gute Haftfestigkeiten, insbesondere bei Zug-Scherbeanspruchung ergeben und die eine gute Wasserwiderstandsfähigkeit haben.It is therefore an object of the present invention to provide binders which are curable at room temperature and which cure in a relatively short time Adhesive strengths, particularly in the case of tensile shear stress, and which have good water resistance.
Die Lösung der Aufgabe erfolgt durch Bindemittel gemäß der Ansprüche 1 bis 4. Diese Bindemittel finden Verwendung als Bindemittel für Dübel- und Ankermassen, für Dicht- und Klebstoffe für die Isolierglasherstellung sowie als Injektionsharze, gemäß der Ansprüche 5 bis 7.The object is achieved by binders according to claims 1 to 4. These binders are used as binders for dowel and anchor compounds, for sealants and adhesives for the production of insulating glass and as injection resins, according to claims 5 to 7.
Es wurde gefunden, daß Gemische aus Epoxidharz mit mindestens zwei Epoxidgruppen im Molekül und Partialester einer Di- oder Polyepoxidverbindung mit einer ethylenisch ungesättigten Säure im Gewichtsverhältnis von 90 : 10 bis 10 : 90, insbesondere von 70 : 30 bis 30 : 70, wenn sie mit einer aminischen Verbindung mit mindestens einer primären Aminogruppe im Molekül gemischt werden, bei Raumtemperatur innerhalb 6 bis 10 h aushärten.It has been found that mixtures of epoxy resin with at least two epoxy groups in the molecule and partial esters of a di- or polyepoxide compound with an ethylenically unsaturated acid in a weight ratio of 90:10 to 10:90, in particular 70:30 to 30:70, when combined with an amine compound with at least one primary amino group in the molecule, cure at room temperature within 6 to 10 h.
Die Mischungen bilden, wenn sie in noch verarbeitbarem Zustand auf einen entsprechenden Untergrund aufgebracht werden, eine ausgezeichnete Haftung zu einer Vielzahl von Substraten aus, wie z. B. zu Glas, Stein, Metall, Holz und Kunststoffen, hier insbesondere zu solchen aus polaren Molekülen, wie z. B. PVC, Polyester, Polyamid, Phenolharz, Epoxidharz oder Polyacrylat.When applied to a suitable substrate in the processable state, the mixtures form excellent adhesion to a large number of substrates, such as, for. B. to glass, stone, metal, wood and plastics, in particular to those made of polar molecules, such as. B. PVC, polyester, polyamide, phenolic resin, epoxy resin or polyacrylate.
Sie eignen sich somit als Bindemittel zum Verkleben gleichartiger Substrate aber auch von Substraten unterschiedlicher Art miteinander. Die Bindemittel haben auch bei mehrstündiger Lagerung in kochendem Wasser eine geringe Wasseraufnahme. Damit ist eine gute Wasserwiderstandsfähigkeit gegeben.They are therefore suitable as binders for bonding substrates of the same type but also substrates of different types to one another. Even when stored in boiling water for several hours, the binders have a low water absorption. This ensures good water resistance.
Als Epoxidharz-Komponente für die Mischung können alle Epoxidverbindungen mit mindestens zwei Epoxidgruppen im Molekül eingesetzt werden. Bevorzugt werden Polyepoxidverbindungen auf der Basis von Bisphenolen oder Phenol- bzw. Kresol-novolaken. Zur Viskositätsregulierung können diesen Harzen difunktionelle aromatische oder aliphatische Epoxidverbindungen, sog. Reaktivverdünner zugesetzt werden.All epoxy compounds with at least two epoxy groups in the molecule can be used as the epoxy resin component for the mixture. Polyepoxide compounds based on bisphenols or phenol or cresol novolaks are preferred. To regulate the viscosity, difunctional aromatic or aliphatic epoxy compounds, so-called reactive thinners, can be added to these resins.
Partialester einer Di- oder Polyepoxidverbindung mit einer ethylenisch ungesättigten Säure sind an sich bekannte Umsetzungsprodukte aus Epoxidverbindungen mit mindestens zwei Epoxidgruppen im Molekül mit einer ethylenisch ungesättigten Säure. Beispiele für derartige Säuren sind Acryl-, Methacryl-, Zimt- oder Furylacrylsäure. Bei dieser an sich bekannten Umsetzung wird das Mengenverhältnis von Epoxidgruppen zu ethylenisch ungesättigter Säure so gewählt, daß der entstehende Partialester im Durchschnitt mindestens eine Epoxid- und eine ethylenisch ungesättigte Gruppe im Molekül enthält.Partial esters of a di- or polyepoxide compound with an ethylenically unsaturated acid are reaction products known per se from epoxy compounds with at least two epoxide groups in the molecule with an ethylenically unsaturated acid. Examples of such acids are acrylic, methacrylic, cinnamon or furylacrylic acid. In this reaction, which is known per se, the quantitative ratio of epoxy groups to ethylenically unsaturated acid is selected so that the partial ester formed contains on average at least one epoxy and one ethylenically unsaturated group in the molecule.
So werden z. B. Diepoxidverbindungen mit 40 bis 50 % der den Epoxidgruppen äquivalenten Menge an ethylenisch ungesättigter Säure umgesetzt. Bei Polyepoxidverbindungen liegt das Molverhältnis Epoxidgruppen zu ethylenisch ungesättigter Säure im Bereich von 2 : 0,5 bis 2 : 1,5.So z. B. Diepoxidverbindungen implemented with 40 to 50% of the epoxy groups equivalent amount of ethylenically unsaturated acid. In the case of polyepoxide compounds, the molar ratio of epoxy groups to ethylenically unsaturated acid is in the range from 2: 0.5 to 2: 1.5.
Epoxidharz und Partialester einer Di- oder Polyepoxidverbindung mit einer ethylenisch ungesättigten Säure werden im Gewichtsverhältnis von 90 : 10 bis 10 : 90, bevorzugt von 70 : 30 bis 30 : 70 miteinander vermischt. Diese Mischungen sind lagerstabil.Epoxy resin and partial esters of a di- or polyepoxide compound with an ethylenically unsaturated acid are mixed with one another in a weight ratio of from 90:10 to 10:90, preferably from 70:30 to 30:70. These mixtures are stable on storage.
Als Härtungsmittel können alle Verbindungen eingesetzt werden, die mindestens eine primäre Aminogruppe enthalten, wie z. B. aliphatische, alicyclische und aromatische Mono-, Di- oder Polyamine aber auch Polyaminoamide. Insbesondere einsetzbar sind die aus der Epoxidharzhärtung bekannten primären Amine, wie sie z. B. auch in Lee und Neville "Handbook of Epoxy Resins", McGraw-Hill Book Company 1967 beschrieben sind.All compounds containing at least one primary amino group, such as. B. aliphatic, alicyclic and aromatic mono-, di- or polyamines but also polyaminoamides. The primary amines known from epoxy resin curing, as used, for. B. also described in Lee and Neville "Handbook of Epoxy Resins", McGraw-Hill Book Company 1967.
Die Aminmenge wird so gewählt, daß für jede ungesättigte Bindung und für jede Epoxidgruppe ein Aminwasserstoffatom zur Verfügung steht.The amount of amine is chosen so that an amine hydrogen atom is available for each unsaturated bond and for each epoxy group.
Nach dem Vermischen des Amins mit dem Gemisch aus Epoxidharz und dem dualfunktionalen Partialester einer Di- oder Polyepoxidverbindung mit einer ethylenisch ungesättigten Säure reagieren in einem ersten Schritt die ethylenisch ungesättigten Doppelbindungen sehr rasch mit dem als Härtungsmittel eingesetzten Amin, und in einem weiteren Schritt reagieren die im gleichen Molekül und die im Epoxidharz vorhandenen Epoxidgruppen ebenfalls mit dem Amin.After mixing the amine with the mixture of epoxy resin and the dual-functional partial ester of a di- or polyepoxide compound with an ethylenically unsaturated acid, the ethylenically unsaturated double bonds react very quickly with the amine used as curing agent, and in a further step the im react same molecule and the epoxy groups present in the epoxy resin also with the amine.
Die spontan einsetzende Reaktion zwischen Amin und Doppelbindung beschleunigt das System soweit, daß schon nach relativ kurzer Zeit ausgezeichnete Haftungswerte erzielt werden. Die geringe Wasseraufnahme, die ähnlich niedrig wie bei den unmodifizierten Epoxidharzsystemen liegt, läßt sich ebenfalls nur über die Doppelfunktionalität erreichen, da hier auch mit aliphatischen Verbindungen ähnlich gute Werte erzielt werden, wie sonst nur mit aromatischen hydrophoben Verbindungen. Aufgrund ihrer Eigenschaften eignen sich die erfindungsgemäßen Bindemittel als Klebstoffe und Bindemittel für Beschichtungen und Spachtelmassen, insbesondere als Bindemittel für Dübel- und Ankermassen, für Dicht- und Klebstoffe für die Isolierglasherstellung sowie als Injektionsharze.The spontaneous reaction between amine and double bond accelerates the system to such an extent that excellent adhesion values are achieved after a relatively short time. The low water absorption, which is similar to that of the unmodified epoxy resin systems, can also only be achieved by means of the double functionality, since similarly good values are achieved with aliphatic compounds as otherwise only with aromatic hydrophobic compounds. Because of their properties, the binders according to the invention are suitable as adhesives and binders for coatings and leveling compounds, especially as binders for dowel and anchor compounds, for sealants and adhesives for insulating glass production and as injection resins.
Bei der praktischen Anwendung können sowohl die Harzals auch die Härterkomponenten mit Füllstoffen, Additiven, Weichmachern oder auch anderen Polymeren vermischt werden. Dadurch können die beiden Komponenten in ihrem Mengenverhältnis so eingestellt werden, daß günstige Mischungsverhältnisse vorliegen.In practical use, both the resin and the hardener components can be mixed with fillers, additives, plasticizers or other polymers. As a result, the proportions of the two components can be adjusted so that there are favorable mixing ratios.
Beispiele für übliche Füllstoffe sind Kreiden, Silicate oder Oxide, bzw. Oxidhydrate der Elemente Aluminium, Magnesium, Silicium oder Titan. Übliche Additive sind Verdickungsmittel, Pigmente oder Silane, insbesondere Epoxisilane, die eine weitere Verbesserung der Haftung, insbesondere auf silikatischen Untergründen bewirken.Examples of common fillers are chalks, silicates or oxides, or oxide hydrates of the elements aluminum, magnesium, silicon or titanium. Common additives are thickeners, pigments or silanes, in particular epoxysilanes, which bring about a further improvement in adhesion, in particular on silicate substrates.
Zusätzliche Polymere sind flüssige merkaptoendständige Polymere, insbesondere solche der allgemeinen Formel
HS-(C₂H₄-O-CH₂-O-C₂H₄-SS) n -C₂H₄-O-CH₂-O-C₂H₄-SH
mit n = 3 bis 8, die bevorzugt der Aminkomponente zugegeben werden sowie Umsetzungsprodukte aus flüssigen, merkaptoendständigen Polymeren mit einem Di- oder Polyacrylat oder - methacrylat, wie sie z. B. aus EP-A 0 502 611 bekannt sind. Beide Polymere, die bis zu 50 % des gesamten Bindemittels darstellen können, erhöhen die Wasser- und die Lösemittelbeständigkeit und bewirken eine Flexibilisierung des Bindemittels.Additional polymers are liquid mercapto-terminal polymers, especially those of the general formula
HS- (C₂H₄-O-CH₂-O-C₂H₄-SS) n -C₂H₄-O-CH₂-O-C₂H₄-SH
with n = 3 to 8, which are preferably added to the amine component, and reaction products of liquid, mercapto-terminal polymers with a di- or polyacrylate or - methacrylate, as described, for. B. are known from EP-A 0 502 611. Both polymers, which can represent up to 50% of the total binder, increase the water and solvent resistance and bring about a flexibilization of the binder.
Erläuterung der Abkürzungen:
- BPA-DGE
- = Diglycidylether des Bisphenols A
- TETA
- = Triethylentretramin
- RT
- = Raumtemperatur
- EP
- = Epoxidharz
- Äqu.
- = Äquivalentgewicht (Aminwasserstoff)
- BPA-DGE
- = Diglycidyl ether of bisphenol A
- TETA
- = Triethylenetretramine
- RT
- = Room temperature
- EP
- = Epoxy resin
- Equ.
- = Equivalent weight (amine hydrogen)
1 Mol Bisphenol F-diglycidylether = 344 g werden mit 3,5 g Triphenylphosphin als Katalysator und 0,1 g Hydrochinon als Inhibitor versetzt und auf 80 °C erhitzt. Unter Einblasen von Luft wird 1 Mol = 72 g Acrylsäure langsam zugetropft. Man läßt so lange bei 80 °C reagieren, bis eine Säurezahl < 5 mg KOH/g erreicht ist.1 mol of bisphenol F-diglycidyl ether = 344 g are mixed with 3.5 g of triphenylphosphine as catalyst and 0.1 g of hydroquinone as inhibitor and heated to 80 ° C. 1 mole = 72 g of acrylic acid is slowly added dropwise while blowing in air. The mixture is left to react at 80 ° C. until an acid number <5 mg KOH / g is reached.
Unter Verwendung von 1 Mol Hexandiglcyidylether = 296 g wird eine aliphatische Epoxiacrylatverbindung analog A hergestellt.An aliphatic epoxy acrylate compound analogous to A is prepared using 1 mol of hexanediglcyidyl ether = 296 g.
Gemische, hergestellt aus Epoxidharz und Partialester (Beispiele 1, 2, 5 und 6) bzw. Polyethylenglykoldiacrylat (Vergleichsbeispiele 3 und 7) oder Phenoxyethylacrylat (Vergleichsbeispiele 4 und 8) sowie unmodifiziertes Epoxidharz (Vergleichsbeispiele 9 und 10) werden mit aminischen Härtern ausgehärtet.Mixtures made from epoxy resin and partial esters (Examples 1, 2, 5 and 6) or polyethylene glycol diacrylate (Comparative Examples 3 and 7) or phenoxyethyl acrylate (Comparative Examples 4 and 8) and unmodified epoxy resin (Comparative Examples 9 and 10) are cured with amine hardeners.
Bestimmt wird die Wasseraufnahme nach 7-tägiger Härtung sowie die Zug-Scher-Haftfestigkeit (nach DIN 53 283) aus Probekörpern gemäß DIN 53 281 aus 1,6 mm dicken Platten aus Luftfahrtaluminium (Al Cu Mg 2pl).The water absorption after 7 days of hardening and the tensile-shear bond strength (in accordance with DIN 53 283) are determined from test specimens in accordance with DIN 53 281 from 1.6 mm thick plates made of aerospace aluminum (Al Cu Mg 2 pl).
Als Basisepoxidharz wird in allen Fällen ein Bisphenol A-diglycidyletherharz mit einem Epoxidäquivalentgewicht von 185 g/Äquivalent verwendet.A bisphenol A diglycidyl ether resin with an epoxy equivalent weight of 185 g / equivalent is used in all cases as the base epoxy resin.
Um einen guten Vergleich der einzelnen Versuche zu ermöglichen, werden jeweils Mischungen aus 2 Mol BPA-DGE = 740 g und der Menge eines
(Meth)acrylat-Modifizierungsmittels hergestellt, in der eine Doppelbindung enthalten ist.In order to enable a good comparison of the individual experiments, mixtures of 2 moles BPA-DGE = 740 g and the amount of one are used
(Meth) acrylate modifier prepared in which a double bond is contained.
Als Härtungsmittel werden
- a) ein Reaktionsprodukt aus Xylelendiamin, Formaldehyd und Phenol (Mannichbase) und
- b) ein Polyaminoamid aus TETA und Tallölfettsäure verwendet.
- a) a reaction product of xylelenediamine, formaldehyde and phenol (Mannich base) and
- b) a polyaminoamide from TETA and tall oil fatty acid is used.
Die folgende Tabelle zeigt die Zusammensetzungen der Mischungen der Beispiele 1 bis 10 und die erhaltenen Ergebnisse.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4330684 | 1993-09-10 | ||
| DE4330684A DE4330684A1 (en) | 1993-09-10 | 1993-09-10 | Curable binders |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0643103A1 true EP0643103A1 (en) | 1995-03-15 |
| EP0643103B1 EP0643103B1 (en) | 1999-07-07 |
Family
ID=6497350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94112176A Expired - Lifetime EP0643103B1 (en) | 1993-09-10 | 1994-08-04 | Curable binders |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0643103B1 (en) |
| AT (1) | ATE181944T1 (en) |
| DE (2) | DE4330684A1 (en) |
| ES (1) | ES2069511T1 (en) |
| GR (1) | GR950300014T1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2716202A1 (en) * | 1994-02-17 | 1995-08-18 | Sandoz Sa | Partially acrylated epoxy compositions curable under the action of an amine. |
| WO2002077059A1 (en) * | 2001-03-22 | 2002-10-03 | Bakelite Ag | Method for the production of reinforcing or laminating materials treated with resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2406400B2 (en) * | 1973-02-14 | 1977-04-28 | Hitachi Chemical Co., Ltd., Tokio | LIGHT-SENSITIVE RESIN COMPOSITIONS ON THE BASIS OF COMPOUNDS WITH EPOXY OR. PHOTOPOLYMERIZABLE ACRYLIC GROUPS |
| EP0237255A2 (en) * | 1986-03-07 | 1987-09-16 | Hitachi, Ltd. | Curable resin compositions and semiconductor devices coated and sealed with the same |
| EP0282634A1 (en) * | 1984-06-26 | 1988-09-21 | Kabushiki Kaisha Toshiba | Photocurable composition |
| EP0502611A2 (en) * | 1991-03-04 | 1992-09-09 | Morton International, Inc. | Rapid gel system in conjunction with epoxy resins |
-
1993
- 1993-09-10 DE DE4330684A patent/DE4330684A1/en not_active Withdrawn
-
1994
- 1994-08-04 EP EP94112176A patent/EP0643103B1/en not_active Expired - Lifetime
- 1994-08-04 AT AT94112176T patent/ATE181944T1/en active
- 1994-08-04 DE DE59408460T patent/DE59408460D1/en not_active Expired - Lifetime
- 1994-08-04 ES ES94112176T patent/ES2069511T1/en active Pending
-
1995
- 1995-04-30 GR GR950300014T patent/GR950300014T1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2406400B2 (en) * | 1973-02-14 | 1977-04-28 | Hitachi Chemical Co., Ltd., Tokio | LIGHT-SENSITIVE RESIN COMPOSITIONS ON THE BASIS OF COMPOUNDS WITH EPOXY OR. PHOTOPOLYMERIZABLE ACRYLIC GROUPS |
| EP0282634A1 (en) * | 1984-06-26 | 1988-09-21 | Kabushiki Kaisha Toshiba | Photocurable composition |
| EP0237255A2 (en) * | 1986-03-07 | 1987-09-16 | Hitachi, Ltd. | Curable resin compositions and semiconductor devices coated and sealed with the same |
| EP0502611A2 (en) * | 1991-03-04 | 1992-09-09 | Morton International, Inc. | Rapid gel system in conjunction with epoxy resins |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2716202A1 (en) * | 1994-02-17 | 1995-08-18 | Sandoz Sa | Partially acrylated epoxy compositions curable under the action of an amine. |
| WO2002077059A1 (en) * | 2001-03-22 | 2002-10-03 | Bakelite Ag | Method for the production of reinforcing or laminating materials treated with resin |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4330684A1 (en) | 1995-03-16 |
| EP0643103B1 (en) | 1999-07-07 |
| ATE181944T1 (en) | 1999-07-15 |
| ES2069511T1 (en) | 1995-05-16 |
| DE59408460D1 (en) | 1999-08-12 |
| GR950300014T1 (en) | 1995-04-30 |
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